Polyolefin resin composition

ABSTRACT

The present invention discloses a polyolefin resin composition comprising a specific cycloolefin-based polymer (a), a graft-modified elastomer (b) and a compound (c) having one amino group in the molecule, and containing, based on the total amount of the components (a), (b) and (c), 50 to 95% by weight of the component (a), 1 to 50% by weight of the component (b) and 0.01 to 45% by weight of the component (c). This polyolefin resin composition is improved particularly in mechanical properties such as impact strength, etc., while retaining excellent properties of the cycloolefin-based polymer (a).

TECHNICAL FIELD

The present invention relates to a polyolefin resin composition. Morespecifically, it relates to a polyolefin resin composition comprising acycloolefin-based polymer (a), a graft-modified elastomer (b) and anamino compound (c) and being excellent in impact resistance.

TECHNICAL BACKGROUND

Conventional polyolefins are resins excellent in chemical resistance andsolvent resistance, but cannot be said to have sufficient rigidity andheat resistance, when their crystallinity is low.

In order to improve polyolefins in heat resistance and rigidity, thereis therefore employed a method in which a nucleating agent is added or apolyolefin in a molten state is gradually cooled to increase thecrystallinity. However, the effect thereof cannot be said to besatisfactory.

Apart from such conventional polyolefins, it is reported that acopolymer obtained by reaction of ethylene with a bulky monomer isexcellent over conventional polyolefins in various properties such asheat resistance, etc. (U.S. Pat. No. 2,883,372 and Japanese PatentPublication No. 14910/1971).

The assignee of the present application already found that a cycloolefinrandom copolymer obtained by copolymerization of a specific cycloolefinas a bulky monomer and ethylene is excellent in heat resistance, thermalaging resistance, solvent resistance, dielectric properties andrigidity. On the basis of this finding, the assignee of the presentapplication has already proposed inventions of random copolymersobtained from specific cycloolefins (Japanese Laid-Open PatentPublications Nos. 168708/1985, 98780/1986, 115912/1986, 115916/1986,120816/1986 and 252407/1987).

DISCLOSURE OF THE INVENTION

It is an object of the present invention to further improve such a resincomposition containing a cycloolefin-based resin as mentioned above inmechanical properties such as impact strength.

It is another object of the present invention to provide a cycloolefinrandom copolymer-containing resin composition being further improvedparticularly in mechanical properties such as impact strength withoutimpairing excellent properties of cycloolefin-based resins.

Other objects and advantages of the present invention will be apparentfrom the following description. According to the present invention, theabove objects and advantages of the present invention are achieved by apolyolefin resin composition comprising:

(a) at least one cycloolefin-based polymer selected from the groupconsisting of a homopolymer (a1) derived from one of cycloolefins of thefollowing formula (I), ##STR1## (wherein n is 0 or 1, m is 0 or apositive integer, q is 0 or 1, each of R¹ to R¹⁸, R^(a) and R^(b) is,independently of the other, an atom or a group selected from the classconsisting of a hydrogen atom, a halogen atom and a hydrocarbon group,

the two of R¹⁵ to R¹⁸ may bond to each other to form a monocyclic orpolycyclic group which may have a double bond, and further, acombination of R¹⁵ and R¹⁶ or a combination of R¹⁷ and R¹⁸ may form analkylidene group),

a copolymer (a2) derived from said cycloolefins, a hydrogenation polymer(a3) of the homopolymer (a1) or the copolymer (a2), and acycloolefin/ethylene random copolymer (a4) composed of a polymer unitderived from said cycloolefins and a polymer unit of ethylene,

(b) an elastomer being graft-modified with an unsaturated carboxylicacid or a derivative thereof and having a tensile modulus, at 23° C., of0.1 to 2,000 kg/cm², and

(c) a compound having one amino group in the molecule,

(d) the polyolefin resin composition containing, per 100 parts by weightof the total amount of the component (a), the component (b) and thecomponent (c), 50 to 95 parts by weight of the component (a), 1 to 50parts by weight of the component (b) and 0.01 to 45 parts by weight ofthe component (c).

The polyolefin resin composition of the present invention basicallycomprises a cycloolefin-based polymer (a), a graft-modified elastomer(b) and a compound (c) having one amino group in the molecule asdescribed above. The composition of the present invention can providemolded articles being improved particularly in mechanical propertiessuch as impact strength and in surface gloss without impairing excellentproperties of cycloolefin-based resins.

The polyolefin resin composition of the present invention will bespecifically described hereinafter.

The polyolefin resin composition according to the present invention is acomposition composed basically of a cycloolefin-based polymer (a), agraft-modified elastomer (b) and a specific, amino group-containingcompound (c).

The component (a) used in the present invention, i.e., thecycloolefin-based polymer, is selected from the class consisting of ahomopolymer (a1) derived from one of cycloolefins of the above formula(I), a copolymer (a2) derived from said cycloolefins, a hydrogenationpolymer of the homopolymer (a1) or the copolymer (a2) and acycloolefin/ethylene random copolymer (a4) composed of a polymer unitderived from said cycloolefins and a polymer unit of ethylene. Thesecycloolefin-based polymers may be used alone or in combination of two ormore.

In the above formula (I), n is 0 or 1, m is 0 or a positive integer, andq is 0 or 1.

Each of R¹ to R¹⁸, R^(a) and R^(b) is, independently of the other, is anatom or a group selected from the class consisting of a hydrogen atom, ahalogen atom and a hydrocarbon group. The halogen atom includes, forexample, a fluorine atom, a chlorine atom, a bromine atom and an iodineatom. The hydrocarbon group preferably includes, for example, an alkylgroup having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 15carbon atoms. Examples of the alkyl group are preferably methyl, ethyl,propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl and octadecyl. Thecycloalkyl group preferably is, for example, cyclohexyl.

In the above formula (I), R¹⁵ and R¹⁶, R¹⁷ and R¹⁸, R¹⁵ and R¹⁷, R¹⁶ andR¹⁸, R¹⁵ and R¹⁸, or R¹⁶ and R¹⁷ may bond to each other (jointly witheach other) to form a monocyclic or polycyclic group. And, thesemonocyclic and polycyclic groups may have a double bond.

Further, R¹⁵ and R¹⁶, or R¹⁷ and R¹⁸ may form an alkylidene group. Suchan alkylidene group preferably includes an alkylidene group having 2 to20 carbon atoms. Examples of such an alkylidene group are preferably anethylidene group, a propylidene group and an isopropylidene group.

The intrinsic viscosity [η] of the above cycloolefin-based resins,measured in decalin at 135° C., is preferably in the range of 0.3 to 2.0dl/g, more preferably in the range of 0.4 to 1.2 dl/g. The softeningtemperature (TMA) thereof, measured with a thermal mechanical analyzer,is preferably in the range of 70° to 200° C., more preferably in therange of 100° to 180° C. Further, the glass transition temperature (Tg)thereof is preferably in the range of 50° to 190° C., preferably in therange of 80° to 170° C., and the crystallinity thereof, measured by anX-ray diffraction method, is preferably in the range of 0 to 20%, morepreferably in the range of 0 to 2%.

Among the above cycloolefin-based resins, the polymer (a1), thecopolymer (a2) and the hydrogenation polymers (a3) of these arebasically formed of ring-opening polymerization polymers derived fromcycloolefins.

The polymer (a1) and the copolymer (a2) can be produced, for example, by(co)polymerizing cycloolefins of the above formula (I) in the presenceof a catalyst comprising any one of a halide of a metal such asruthenium, rhodium, palladium, osmium, indium or platinum; nitrate; andan acetylacetone compound and a reducing agent; or

a catalyst comprising either a halide of a metal such as titanium,palladium, zirconium or molybdenum or an acetylacetone compound and anorganoaluminum.

The hydrogenation polymer (a3) can be produced, for example, by reducingthe above-obtained ring-opening polymerization polymer of a cycloolefin,(a1) or (a2), with hydrogen in the presence of a hydrogenating catalyst.

The cycloolefin/ethylene random copolymer (a4) can be produced, forexample, by copolymerizing ethylene and an unsaturated monomer of theabove formula (I) in a liquid phase in the presence of a catalyst.

The cycloolefins of the above formula (I) can be easily produced bycondensing cyclopentadienes and corresponding olefins or correspondingcycloolefins under a Diels-Alder reaction.

That is, the cycloolefins of the above formula (I), used in the presentinvention, specifically include the following compounds:

Bicyclo[2.2.1]hept-2-enes,

Tetraccyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecenes,

Hexacyclo[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14 ]-4-heptadecenes,

Octacyclo[8.8.0.1²,9.1⁴,7.1¹¹,18.1¹³,16.0³,8.0.sup.12,17 ]-5-docosenes,

Pentacyclo[6.6.1.1³,6.0²,7.0⁹,14 ]-4-hexadecenes,

Heptacyclo-5-eicosenes,

Heptacyclo-5-heneicosenes,

Tricyclo[4.3.0.1²,5 ]-3-decenes,

Tricyclo[4.4.0.1²,5 ]-3-undecenes,

Pentacyclo[6.5.1.1³,6.0²,7.0⁹,13 ]-4-pentadecenes,

Pentacyclopentadecadienes,

Pentacyclo[4.7.0.1²,5.0⁸.13.1⁹,12 ]-3-pentadecenes,

Heptacyclo[7.8.0.1³,6.0²,7.1¹⁰,17.0¹¹,16.1¹²,15 ]-4-eicosenes,

Nonacyclo[9.10.1.1⁴,7.0³,8. . . .0²,10.0¹²,21.1¹³,20.0¹⁴,19.1¹⁵,18]-5-pentacosenes,

Petacyclo[4.8.4²,5.0⁸,13.1⁹,12 ]-3-hexadecenes,

Heptacyclo[8.8.0.0³,8.1⁴,7.1¹¹,18.0¹²,17.1¹³,16 ]-5-heneicosenes, and

Nonacyclo[10.10.1.0²,11.0⁴,9.1⁵,8.0¹³,22.1¹⁴,21.0.sup.15,20.1¹⁶,19]-6-hexacosenes.

Specific examples of the above compounds are as follows:

Bicyclo[2.2.1]hept-2-enes;

bicyclo[2.2.1]hept-2-ene ##STR2## 6-methylbicyclo[2.2.1]hept-2-ene,5,6-dimethylbicyclo[2.2.1]hept-2-ene,

1-methylbicyclo[2.2.1]hept-2-ene,

6-ethylbicyclo[2.2.1]hept-2-ene,

6-n-butylbicylo[2.2.1]hept-2-ene,

6-isobutylbicyclo[2.2.1]hept-2-ene, and

7-methylbicyclo[2.2.1]hept-2-ene:

Tetraccyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecenes;

tetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene ##STR3##5,10-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,2,10-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

11,12-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

2,7,9-triemthyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

9-ethyl-2,7-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

9-isobutyl-2,7-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

9,11,12-trimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

9-ethyl-11,12-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

9-isobutyl-11,12-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

5,8,9,10-tetramethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-methyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-propyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-hexyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-stearyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8,9-dimethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethyl-9-methyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-chlorotetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-bromotetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-fluorotetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8,9dichlorotetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-cyclohexyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-isobutyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-butyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethylidenetetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethylidene-9-methyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethylidene-9-ethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethylidene-9-isopropyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-ethylidene-9-butyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-n-propylidenetetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-n-propylidene-9-methyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-n-propylidene-9-ethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-n-propylidene-9-isopropyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-n-propylidene-9-butyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-isopropylidenetetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-isopropylidene-9-methyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-isopropylidene-9-ethyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-isopropylidene-9-isopropyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene,

8-isopropylidene-9-butyltetracyclo[4.4.0.1²,5.1⁷,10 ]-3-dodecene:

Hexacyclo[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14 ]-4-heptadecene;

hexacyclo[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14 ]-4-heptadecene ##STR4##12-methylhexacyclo-[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14 ]-4-heptadecene,

12-ethylhexacyclo-[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14 ]-4-heptadecene,

12-isobutylhexacyclo-[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14 ]-4-heptadecene, and

1,6,10-trimethyl-12-isobutylhexacyclo[6.6.1.1³,6.1¹⁰,13.0²,7.0⁹,14]-4-heptadecene:

Octacyclo[8.8.0.1²,9.1⁴,7.1¹¹,18.1¹³,16.0³,8.0.sup.12,17 ]-5-docosenes;

octacyclo[8.8.0.1²,9.1⁴,7.1¹¹,18.1¹³,16.0³,8.0.sup.12,17 ]-5-docosene##STR5##15-methyloctacyclo[8.8.0.1²,9.1⁴,7.1¹¹,18.1¹³,16.0.sup.3,8.0¹²,17]-5-docosene,

15-ethyloctacyclo[8.8.0.1²,9.1⁴,7.1¹¹,18.1¹³,16.0³,8.0¹²,17]-5-docosene:

Pentacyclo[6.6.1.1³,6.0²,7.0⁹,14 ]-4-hexadecenes;

pentacyclo[6.6.1.1³,6.0²,7.0⁹,14 ]-4-hexadecene ##STR6##1,3-dimethylpentacyclo[6.6.1.1³,6.0²,7.0⁹,14 ]-4-hexadecene,

1,6-dimethylpentacyclo[6.6.1.1³,6.0²,7.0⁹,14 ]-4-hexadecene,

15,16-dimethylpentacyclo[6.6.1.1³,6.0²,7.0⁹,14 ]-4-hexadecene:

Heptacyclo-5-eicosenes;

heptacyclo[8.7.0.1²,9.1⁴,7.1¹¹,17.0³,8.0¹²,16 ]-5-eicosene ##STR7##Heptacyclo-5-heneicosens; heptacyclo[8.8.0.1²,9.1⁴,7.1¹¹,18.0³,8.0¹²,17]-5-heneicosene ##STR8## Tricyclo[4.3.0.1²,5 ]-3-decenes;tricyclo[4.3.0.1²,5 ]-3-decene ##STR9## 2-methyltricyclo[4.3.0.1²,5]-3-decene, 5-methyltricyclo[4.3.0.1²,5 ]-3-decene:

Tricyclo[4.4.0.1²,5 ]-3-undecenes;

tricyclo[4.4.0.1²,5 ]-3-undecene ##STR10## 10-methyl-tricyclo[4.4.0.1²,5]-3-undecene: Pentacyclo[6.5.1.1³,6.0²,7.0⁹,13 ]-4-pentadecenes;

pentacyclo[6.5.1.1³,6.0²,7.0⁹,13 ]-4-pentadecene ##STR11##1,3-dimethyl-pentacyclo[6.5.1.1³,6.0²,7.0⁹,13 ]-4-pentadecene,

1,6-dimethylpentacyclo[6.5.1.1³,6.0²,7.0⁹,13 ]-4-pentadecene,

14,15-dimethylpentacyclo[6.5.1.1³,6.0²,7.0⁹,13 ]-4-pentadecene:

Pentacyclopentadecadienes;

pentacyclo[6.5.1.1³,6.0²,7.0⁹,13 ]-4,10-pentadecadiene ##STR12##Pentacyclo[4.7.0.1²,5.0⁸.13.1⁹,12 ]-3-pentadecenes;pentacyclo[4.7.0.1²,5.0⁸.13.1⁹,12 ]-3-pentadecene ##STR13##methyl-substituted pentacyclo[4.7.0.1²,5.0⁸.13.1⁹,12 ]-3-pentadecene:

Heptacyclo[7.8.0.1³,6.0²,7.1¹⁰,17.0¹¹,16.1¹²,15 ]-4-eicosenes;

heptacyclo[7.8.0.1³,6.0²,7.1¹⁰,17.0¹¹,16.1¹²,15 ]-4-eicosene ##STR14##dimethyl-substituted heptacyclo[7.8.0.1³,6.0²,7.1¹⁰,17.0¹¹,16.1¹²,15]-4-eicosene:

Nonacyclo[9.10.1.1.⁴.7.0³,8.0²,10.0¹²,21.1¹³,20.0.sup.14,19.1¹⁵,18]-5-pentacosenes;

nonacyclo[9.10.1.1.⁴.7.0³,8.0²,10.0¹²,21.1¹³,20.0.sup.14,19.1¹⁵,18]-5-pentacosene ##STR15## trimethyl-substitutednonacyclo[9.10.1.1.⁴.7.0³,8.0²,10.0¹²,21.1¹³,20.0¹⁴,19.1¹⁵,18]-5-pentacosene:

Pentacyclo[4.8.4²,5.0⁸,13.1⁹,12 ]-3-hexadecenes;

pentacyclo[4.8.4²,5.0⁸,13.1⁹,12 ]-3-hexadecene ##STR16##10-methyl-pentacyclo[4.8.4²,5.0⁸,13.1⁹,12 ]-3-hexadecene,10-ethyl-pentacyclo[4.8.4²,5.0⁸,13.1⁹,12 ]-3-hexadecene,

10,11-dimethyl-pentacyclo[4.8.4²,5.0⁸,13.1⁹,12 ]-3-hexadecene:

Heptacyclo[8.8.0.0³,8.1⁴,7.1¹¹,18.0¹²,17.1¹³,16 ]-5-heneicosenes;

heptacyclo[8.8.0.0³,8.1⁴,7.1¹¹,18.0¹²,17.1¹³,16 ]-5-heneicosene##STR17##14-methyl-heptacyclo[8.8.0.0³,8.1⁴,7.1¹¹,18.0¹²,17.1.sup.13,16]-5-heneicosene,

trimethyl-heptacyclo[8.8.0.0³,8.1⁴,7.1¹¹,18.0¹²,17.1.sup.13,16]-5-heneicosene:

Nonacyclo[10.10.1.0²,11.0⁴,9.1⁵,8.0¹³,22.1¹⁴,21.0.sup.15,20.1¹⁶,19]-6-hexacosenes;

nonacyclo[10.10.1.0²,11.0⁴,9.1⁵,8.0¹³,22.1¹⁴,21.0.sup.15,20.1¹⁶,19]-6-hexacosene ##STR18##

The cycloolefin/ethylene random copolymer (a4) can be obtained bycopolymerizing a cycloolefin of the above formula (I), ethylene andoptionally, other olefin compound.

The other olefin compound copolymerizable with ethylene and thecycloolefin compound of the above formula (I) in the present inventionis selected from α-olefins having 3 to 20 carbon atoms such aspropylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene;

cycloolefins such as cyclopentene, cyclohexene, 3-methylcyclohexene,cyclooctene, and 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene;

conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene,5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene,5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene; and

norbornenes such as norbornene-2, 5-methylnorbornene-2,5-ethylnorbornene-2, 5-isopropylnorbornene-2, 5-n-butylnorbornene-2,5-i-butylnorbornene-2, 5,6-dimethylnorbornene-2, 5-chloronorbornene-2,2-fluoronorbornene-2, and 5,6-dichloronorbornene-2.

The above "other olefin" is used in an amount, based on the total amountof the cycloolefin, ethylene and this other olefin, of preferably notmore than about 20 mol %, more preferably not more than 10 mol %.

The above reaction of ethylene, the cycloolefin of the formula (I) andoptionally other olefin is generally carried out in a hydrocarbonsolvent. The hydrocarbon solvent used in this reaction is selected, forexample, from aliphatic hydrocarbons such as hexane, heptane, octane andkerosene; alicyclic hydrocarbons such as cyclohexane andmethylcyclohexane; and aromatic hydrocarbons such as benzene, tolueneand xylene. Further, polymerizable unsaturated monomers which can beused for the preparation of the cycloolefin random copolymer and whichare liquid compounds at a reaction temperature may be used as a reactionsolvent. These solvents may be used alone or in combination.

The catalyst used for the reaction of the above olefin with thecycloolefin of the formula (I) is selected from catalysts comprisingvanadium compounds soluble in a hydrocarbon solvent used as a reactionsolvent and organoaluminum compounds.

Examples of the vanadium compounds used as a catalyst are compounds ofthe formula, VO(OR)_(a) V_(b) or the formula, V(OR)_(c) X_(d).

In the above formulae, R is a hydrocarbon group, and there are relationsof 0≦a≦3, 0≦b≦3, 2≦a+b≦3, 0≦c≦4, 0≦d≦4 and 3≦c+d≦4.

Further, the vanadium compounds may be adducts of vanadium compounds ofthe above formulae with electron donors.

Examples of the above vanadium compounds are:

VOCl₃,

VO(OC₂ H₅)Cl₂,

VO(OC₂ H₅)₂ Cl,

VO(O--iso--C₃ H₇)Cl₂,

VO(O--n--C₄ H₉)Cl₂,

VO(OC₂ H₅)₃,

VOBr₂,

VCl₄,

VOCl₂,

VO(O--n--C₄ H₉)₃, and

VCl₃.2(OC₈ H₁₇ OH).

These vanadium compounds may be used alone or in combination.

Examples of the electron donors which form adducts with the abovevanadium compounds are oxygen-containing electron donors such asalcohol, phenols, ketone, aldehyde, carboxylic acid, organic orinorganic acid ester, ether, acid amide, acid anhydride, andalkoxysilane, and nitrogen-containing electron donors such as ammonia,amine, nitrile and isocyanate.

Specific compound usable as such an electron donor is selected from:

alcohols having 1 to 18 carbon atoms such as methanol, ethanol,propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol,oleyl alcohol, benzyl alcohol, phenyl ethyl alcohol, cumyl alcohol,isopropyl alcohol, and isopropylbenzyl alcohol;

phenols having 6 to 20 carbon atoms such as phenol, cresol, xylenol,ethylphenol, propylphenol, nonylphenyl, cumylphenol, and naphthol (thesephenols may have a lower alkyl group);

ketones having 3 to 15 carbon atoms such as acetone, methyl ethylketone, methyl isobutyl ketone, acetophenone, benzophenone, andbenzoquinone;

aldehydes having 2 to 15 carbon atoms such as acetaldehyde,propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, andnaphthoaldehyde;

organic acid esters having 2 to 30 carbon atoms such as methyl formate,methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octylacetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethylvalerate, methyl chloroacetate, ethyl dichloroacetate, methylmethacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methylbenzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octylbenzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyltoluylate, ethyl toluylate, amyl toluylate, ethyl ethylbenzoate, methylanisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexylcyclohexenecarboxylate, diethyl Nadic acid ester, diisopropyltetrahydrophthalate, diethyl phthalate, di-n-butyl phthalate,di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin,phthalide, and ethylene carbonate;

acid halides having 2 to 15 carbon atoms such as acetyl chloride,benzoyl chloride, toluic acid chloride, and anisic acid chloride;

ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether,isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, anddiphenyl ether;

acid amides such as acetic amide, benzoic amide, and toluic amide,

amines such as methylamine, ethylamine, diethylamine, tributylamine,piperidine, tribenzylamine, aniline, pyridine, picoline, andtetramethylenediamine;

nitriles such as acetonitrile, benzonitrile, and tolunitrile; and

alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. Theseelectron donors may be used alone or in combination.

The organoaluminum compounds usable in the above reaction have at leastone Al-carbon bond in the molecule.

Examples of the organoaluminum compounds used above are:

(i) organoaluminum compounds of the formula, R²¹ _(e) Al(OR²²)_(f) H_(g)X_(h),

(wherein each of R²¹ and R²² is, independently of the other, ahydrocarbon group which generally has 1 to 15 carbon atoms, preferablyhas 1 to 4 carbon atoms, X is a halogen, e is defined by 0≦e≦3, f isdefined by 0≦f<3, g is defined by 0≦g<3, h is defined by 0≦h<3, ande+f+g+h=3), and

(ii) alkylation product complexes of a Group 1 metal and aluminum, ofthe formula, M¹ AlR²¹ ₄,

(wherein M¹ is Li, Na or K and R²¹ is as defined above).

Specific examples of the organoaluminum compounds of the above formula(i) are as follows.

Compounds of the formula, R²¹ _(i) Al(OR²²)_(3-i),

(wherein R²¹ and R²² are as defined above, and i is preferably a numberdefined by 1.5≦i<3).

Compounds of the formula, R²¹ _(e) AlX_(3-e),

(wherein R²¹ is as defined above, X is a halogen, e is preferablydefined by 0<e<3).

Compounds of the formula, R²¹ _(j) AlH_(3-j),

(wherein R²¹ is as defined above, and j is preferably defined by 2≦j<3).

Compounds of the formula, R²¹ _(e) Al(OR²²)_(f) X_(h),

(wherein R²¹ and R²² are as defined above, X is a halogen, 0<e≦3, 0≦f<3,0≦h<3, and e+f+H=3).

Specific examples of the organoaluminum compounds of the above formula(II) are:

trialkylaluminum such as triethylaluminum and tributylaluminum;

trialkylaluminum such as triisopropylaluminum,

dialkylaluminum alkoxides such as diethylaluminum ethoxide, anddibutylaluminum butoxide;

alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, andbutylaluminum sesquibutoxide;

partially alkoxylated alkylaluminum having an average composition of theformula, R²¹ ₂.5 Al(OR²²)₀.5, etc;

dialkylaluminum halides such as diethylaluminum chloride,dibutylaluminum chloride, and diethylaluminum bromide;

alkylaluminum sesquihalides such as ethylaluminum sesquichloride,butylaluminum sesquichloride, and ethylaluminum sesquibromide;

partially halogenated alkylaluminum such as ethylaluminum dichloride,propylaluminum dichloride, and butylaluminum dibromide;

dialkylaluminum hydrides such as diethylaluminum hydride anddibutylaluminum hydride;

partially hydrogenated alkylaluminum such as alkylaluminum dihydrides,e.g., ethylaluminum dihydride and propylaluminum dihydride; and

partially alkoxylated and halogenated alkylaluminum such asethylaluminum ethoxychloride, butylaluminum butoxychloride, andethylaluminum ethoxybromide.

The organoaluminum compound may also be a compound similar to thecompounds of the formula (ii) such as aluminum compounds in which two ormore aluminum atoms are bonded through an oxygen atom or a nitrogenatom. Specific examples of such a compound are: ##STR19##

Examples of the organoaluminum compounds of the formula (ii) are:

    LiAl(C.sub.2 H.sub.5).sub.4

    and

    LiAl(C.sub.7 H.sub.15).sub.4.

of these, it is preferred to use alkylaluminum halide, alkylaluminumdihalide or a mixture of these.

The amount, as a vanadium atom, of the above vanadium compound for useis generally in the range of 0.01 to 5 gram-atom/lit., preferably in therange of 0.05 to 3 gram-atom/lit. The amount of the organoaluminumcompound, as a ratio of an aluminum atom to a vanadium atom (Al/V) in apolymerization reaction system, is generally not less than 2, preferably2 to 50, particularly preferably 3 to 20.

The cycloolefin-based polymer (a) obtained in the presence of the abovecatalyst contains preferably 52 to 90 mol %, more preferably 55 to 80mol % of an ethylene component unit, and it contains preferably 10 to 48mol %, more preferably 20 to 45 mol % of a recurring unit derived fromthe cycloolefin. In addition, when the cycloolefin-based polymer (a)contains an olefin component unit other than the ethylene componentunit, the content of this olefin component unit in the cycloolefin-basedpolymer is preferably not more than 20 mol %, more preferably not morethan 10 mol %.

In the cycloolefin-based polymer (a) used in the present invention, theethylene component unit and the recurring one derived from thecycloolefin are substantially linearly arranged, and further theserecurring units are arranged at random.

In the cycloolefin-based polymer (a) used in the present invention, therecurring unit which constitutes the alicyclic structure has a structureof the following formula (II), ##STR20## wherein R¹ to R¹⁸, n, m and qare as defined in the above formula (I).

The above cycloolefin-based polymer is incorporated in an amount in therange of 50 to 95 parts by weight per 100 parts by weight of the totalamount of the component (a), the component (b) and the component (c). Inparticular, it is preferred to adjust this amount to the range of 60 to85 parts by weight.

When the component (a) is incorporated in the above amount, there can beobtained a resin composition which is improved in mechanical propertiessuch as impact strength, etc., without impairing excellent properties ofthe cycloolefin-based polymer (a).

The graft-modified elastomer (b) used in the present invention is anelastomer which is obtained by graft-modification with an unsaturatedcarboxylic acid or a derivative thereof and has a tensile modulus, at23° C., of 0.1 to 2,000 kg/cm². The tensile modulus is preferably in therange of 1 to 1,500 kg/cm². The glass transition temperature (Tg) ofthis graft-modified elastomer is preferably in the range of -150° to+50° C., more preferably in the range of -80° to -20° C. The intrinsicviscosity [η], measured in decalin at 135° C., of this graft-modifiedelastomer is preferably 0.2 to 10 dl/g, more preferably 1 to 5 dl/g. Thedensity thereof is preferably 0.82 to 0.96 g/cm³, more preferably 0.84to 0.92 g/cm³. Further, the crystallinity, measured by an X-raydiffraction method, of this graft-modified elastomer is preferably notmore than 30%, more preferably not more than 25%.

When the graft-modified elastomer (b) used in the present invention is agraft-modified α-olefin copolymer, specific examples of thegraft-modified α-olefin copolymer are:

(i) graft-modified ethylene.α-olefin copolymer rubber, and

(ii) graft-modified propylene.α-olefin copolymer rubber. The abovegraft-modified ethylene.α-olefin copolymer rubber (i) and graft-modifiedpropylene.α-olefin copolymer rubber (ii) may be used alone or incombination.

The α-olefin to constitute the above graft-modified ethylene.α-olefincopolymer rubber (i) is generally selected from α-olefins having 3 to 20carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-octene, 1-decene and mixtures of these. Of these,particularly preferred are propylene and/or 1-butene.

The α-olefin to constitute the graft-modified propylene.α-olefincopolymer rubber (ii) is generally selected from α-olefins having 4 to20 carbon atoms such as 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-octene, 1-decene and mixtures of these. Of these,particularly preferred is 1-butene.

In addition, the α-olefin copolymer used in the present invention maycontain a component unit other than the unit derived from the α-olefin,such as a component unit derived from a diene compound, in such anamount that does not impair the properties of the α-olefin copolymer.

Examples of the component unit which may be contained in the α-olefincopolymer used in the present invention are linear non-conjugated dienessuch as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene,6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene;

cyclic non-conjugated dienes such as cyclohexadiene, dicyclopentadiene,methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-norbornene,5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, and6-chloromethyl-5-isopropenyl-2-norbornene;

components units derived from diene compounds such as2,3-diisopropylidene-5-norbornene,2-ethylidene-3-isopropylidene-5-norbornene, and2-propenyl-2,2-norbornadiene; and

the above cycloolefin components. The content of the above dienecomponent is preferably not more than 10 mol %, more preferably not morethan 5 mol %.

In the graft-modified ethylene.α-olefin copolymer (i) used in thepresent invention, although differing depending upon the kind of theα-olefin, the molar ratio of ethylene to the α-olefin(ethylene/α-olefin) is preferably 10/90 to 90/10, more preferably 50/50to 90/10. When the α-olefin is propylene, the above molar ratio ispreferably 50/50 to 90/10. When the α-olefin is an α-olefin having 4 ormore carbon atoms, the above molar ratio is preferably 50/50 to 90/10.

In the graft-modified propylene.α-olefin copolymer (ii) used in thepresent invention, although differing depending upon the kind of theα-olefin, the molar ratio of propylene to the α-olefin(propylene/α-olefin) is, in general, preferably 50/50 to 90/10. When theα-olefin is 1-butene, the above molar ratio is preferably 50/50 to90/10. When the α-olefin is an α-olefin having 5 or more carbon atoms,it is preferably 50/50 to 90/10.

In the present invention, it is preferred to select, out of the abovegraft-modified elastomers (b), a copolymer obtained bygraft-modification of an ethylene propylene random copolymer orethylene.α-olefin random copolymer having an ethylene content of 35 to50 mol % and a crystallinity of not more than 10% with a graft monomer,since such a copolymer has an excellent effect on improvement ofmechanical properties such as impact strength.

The graft monomer used for the preparation of the graft-modifiedelastomer (b) used in the present invention is selected from unsaturatedcarboxylic acids or derivatives thereof. Examples of the unsaturatedcarboxylic acid are acrylic acid, maleic acid, fumaric acid,tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid,isocrotonic acid, and Nadic acid®(endo-cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid). Examples ofthe derivatives of the above unsaturated carboxylic acid are unsaturatedcarboxylic acid anhydrides, unsaturated carboxylic acid halides,unsaturated carboxylic acid amides, unsaturated carboxylic acid imidesand ester compounds of unsaturated carboxylic acids. Specific examplesof these derivatives are malenyl chloride, maleimide, maleic anhydride,citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidylmeleate, glycidyl acrylate, and glycidyl methacrylate.

These graft monomers may be used alone or in combination.

Of the above graft monomers, preferred are unsaturated carboxylic acidsor anhydrides thereof, and particularly preferred are maleic acid, Nadicacid® and anhydrides of these or glycidyl methacrylate and glycidylacrylate.

The graft-modified elastomer (b) used in the present invention can beprepared, for example, by modifying the α-olefin copolymer with theabove graft monomer by any one of various known methods. For example,there is available a method in which the above α-olefin copolymer ismelted and the graft monomer is added thereto for graft polymerization,or a method in which the graft monomer dissolved in a solvent is addedfor graft polymerization. Further, the graft-modified elastomer can bealso prepared by other method in which the graft monomer is incorporatedinto an unmodified α-olefin copolymer such that the α-olefin copolymerhas a desired graft modification ratio, or in which a graft-modifiedα-olefin having a high graft modification ratio is prelimiarily preparedand this α-olefin copolymer having a high graft modification ratio isdiluted with an unmodified α-olefin copolymer to prepare agraft-modified elastomer having a desired modification ratio. In thepresent invention, a graft-modified elastomer prepared by any one of theabove methods may be used. The graft-modified elastomer (b) used in thepresent invention is a copolymer having a graft modification ratio inthe range of preferably 0.01 to 5% by weight, more preferably 0.1 to 4%by weight.

The above reaction is carried out preferably in the presence of aradical initiator in order to effectively carry out the graftcopolymerization with the above graft monomer. The graft reaction isgenerally carried out at a temperature between 60° C. and 350° C. Theamount of the radical initiator for use is generally in the range of0.001 to 5 parts by weight per 100 parts by weight of the unmodifiedα-olefin elastomeric copolymer.

As the radical initiator, organic peroxides and organic peresters can bepreferably used. Specific examples of these radical initiators arebenzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide,di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxidebenzoate)hexyne-3,1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tertbutylperacetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert-butyloxy)hexane, tert-butyl perbenzoate,tert-butylperphenyl acetate, tert-butyl perisobutylate, tert-butylper-sec-octoate, tert-butyl perpivalate, cumyl perpivalate, andtert-butyl perdiethylacetate. In the present invention, further, an azocompound may be used as a radical initiator. Specific examples of theazo compound are azobisisobutyronitrile and dimethylazoisobutyrate.

Of these, preferred as the radical initiator are dialkyl peroxides suchas benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide,2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane and1,4-bis(tert-butylperoxyisopropyl)benzene.

As the graft-modified elastomer (b) used in the present invention, theabove graft-modified ethylene.α-olefin copolymer (i) and the abovegraft-modified propylene.α-olefin copolymer (ii) are generally usedalone or in combination. However, other polymer, copolymer or graftcopolymer may be used in combination in such an amount that does notimpair the properties of the graft-modified elastomer.

Examples of the above "other polymer or copolymer" in the presentinvention are aromatic vinyl-containing hydrocarbon.conjugated dienecopolymers or hydrides thereof. Specific examples of the aromaticvinyl-containing hydrocarbon.conjugated diene copolymers or the hydridesthereof are styrene.butadiene copolymer rubber,styrene.butadiene.styrene copolymer rubber, styrene.isoprene blockcopolymer rubber, styrene.isoprene.styrene block copolymer rubber,hydrogenated styrene.butadiene.styrene block copolymer rubber andhydrogenated styrene.isoprene.styrene block copolymer rubber.

The above graft-modified elastomer (b) is incorporated in an amount inthe range of 1 to 50 parts by weight per 100 parts by weight of thetotal amount of the component (a), the component (b) and the component(c). It is particularly preferred to adjust this amount to the range of10 to 30 parts by weight.

When the component (b) in the above amount is incorporated, there can beobtained a resin composition which is improved in mechanical propertiessuch as impact strength without impairing excellent properties of thecycloolefin-based polymer (a).

The polyolefin resin composition of the present invention contains, as acomponent (c), a compound having one amino group in the molecule. Theconcept of "compound" used here includes a condensate, a ring-openingreaction product and a high-molecular-weight compound.

In the present invention, the following compounds are suitably usable asa component (c).

(C1) a condensate having one amino group in the molecule.

(C2) a ring-opening reaction product having one amino group in themolecule.

(C3) a polymer in which one amino group is bonded to a polyolefin havinga molecular weight of not less than 20,000.

(C4) a low-molecular-weight amino compound in which one of the moleculeterminals is an amino group.

That is, the condensate (C1) used as a component (c) in the presentinvention is a product formed by a condensation reaction, and refersmainly to an oligomer or polymer of an aminocarboxylic acid. Thering-opening reaction product (C2) is a product formed by a ring-openingreaction and refers mainly to a ring-opening polymerization polymer fromlactams. Further, the polymer (C3) is a polymer in which one amino groupis bonded to a polyolefin having a molecular weight of not less than20,000. The low-molecular-weight amino compound (C4) having one aminogroup in the molecule refers mainly to a monomer used for thepreparation of the above condensate (C1) or the above ring-openingreaction product (C2).

In the present invention, as a component (c), the component (C1), thecomponent (C2), the component (C3) and the component (C4) may be usedalone or as a mixture of at least two of these.

In the present invention, as a compound which is particularly effectiveas the low-molecular-weight amino compound (C-4) in which one of themolecule terminals is an amino group, used as a component (c), there isa compound of the following formula (C4a) or (C4b). ##STR21##

In the above formulae (C4a) and (C4b), R²³ is an alkylene group.

Specific examples of the above low-molecular-weight amino compound areε-aminocaproic acid, 7-aminoheptanoic acid, ω-aminoundecanoic acid,laurolactam, ω-aminononanoic acid, β-propiolactam, 2-piperidone,γ-butyrolactam, 11-aminoundecanoic acid, α-pyrropydone, γ-aminobutyricacid, β-alanine, 8-aminovaleric acid, and ε-aminolactam.

Examples of the amino group-containing condensate (C1) or thering-opening reaction product (C2) are preferably compounds orring-opening polymerization polymers (or polycondensation polymers)formed by condensation reactions of compounds containing an amino groupand a carboxyl group, which can have (or have) an amino group and acarboxyl group, such as an aminocarboxylic acid, or a dicarboxylic acidwith a diamine, or ε-aminocaprolactam, or functional derivativesthereof.

Typical examples of the amino group-containing condensate (C1) arepolyamide precursors and polyamide resins. Examples of the polyamideprecursors are aliphatic amines such as ethylenediamine,propylenediamine, hexamethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylenepentamine, iminobispropylamine,bis(hexamethylene)triamine, 1,3,6-trisaminomethylhexane,trimethylhexamethylenediamine, bispropylenediamine, anddiethylaminopropylamine;

alicyclic amines such as menthenediamine, isophoronediamine,bis(4-amino-3-methylcyclohexyl)methane, N-aminoethylpiperazine, and1,3-diaminocyclohexane;

aliphatic aromatic amines such as m-xylylenediamine;

aromatic amines such as o-, m- or p-phenylenediamine,diaminodiphenylmethane, diaminodiphenylsulfone, 2,4-diaminoanisole,2,4-toluenediamine, 2,4-diaminidiphenylamine, 4,4'-methylenedianiline,and diaminodixylylsulfone;

oligomers formed by polycondensation of diamine components such asbisspiro-cyclized diamines, e.g.,3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro[5,5]undecane withdicarboxylic acids such as adipic acid, sebacic acid, terephthalic acid,isophthalic acid, dodecanoic diacid, and glutaric acid; and

oligomers formed by ring-opening polymerization or polycondensation ofε-caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid,and 11-aminoundecanoic acid.

In the present invention, the "oligomer" refers to the above condensateor ring-opening polymerization product having a molecular weight of lessthan 2,000.

Examples of the polyamide resins are those which are condensates of theabove diamine components and either the above dicarboxylic acidcomponents or ε-aminoundecanoic acid and ring-opening polymerizationpolymers of the above lactams and have a molecular weight of not lessthan 2,000. Specific examples thereof are nylon-2, nylon-3, nylon-4,nylon-5, nylon-6, nylon-7, nylon-8, nylon-9, nylon-10, nylon-11,nylon-12, nylon-13, nylon-66, nylon-610, nylon-612, copolymer nylonformed from caprolactam and a nylon salt aqueous solution, nylon MXD6formed from m-xylylenediamine and adipic acid, nylon-46, andmethoxymethylated polyamide.

In the present invention, the above oligomers and polyamides may be usedalone or in combination.

Of these, preferred are polyamide resins which have an amino group onone terminal and are crystalline, such as nylon 6, nylon 11 and nylon12.

The polymer (C3) in which one amino group is bonded to a polyolefinhaving a molecular weight of not less than 20,000 refers, for example,to a polymer in which one amino group is bonded to a polymer of anα-olefin such as ethylene or propylene. Such a polymer (C3) can beprepared by introducing an amino group to a polyolefin according to aknown method.

The above compound (c) having an amino group is incorporated in anamount of 0.01 to 45 parts by weight per 100 parts by weight of thetotal amount of the component (a), the component (b) and the component(c). It is particularly preferred to adjust this amount to the range of0.01 to 30 parts by weight.

Owing to the incorporation of the compound (c) having an amino group,there can be formed a molded article which is excellent particularly inimpact strength and gloss. That is, these components (C1), (C2) and (C3)has relatively high crystallinity around room temperature, and due tothis crystallinity, the cycloolefin-based resin is improved inproperties. The component (C4) in the composition also works in the sameway as the components (C1), (C2) and (C3). It is considered that when byincorporation of this compound (c) having an amino group, the compound(c) exhibits a reinforcing effect since its crystal has an effectsimilar to that of a crosslinking agent at a temperature not higher thanthe melting point of this compound to form a crosslinked structure-likestructure in the graft-modified copolymer, and that the compositionexhibits excellent moldability since with an increase in temperature,the reinforcing effect due to the structure similar to a crosslinkedstructure decreases and the composition gradually has excellentflowability.

In addition to the above components, the polyolefin resin composition ofthe present invention may contain additives such as an inorganic filler,an organic filler, a thermal stabilizer, a weathering stabilizer, anantistatic agent, an anti-slipping agent, an antiblocking agent, ananti-fogging agent, a lubricant, a pigment, a dye, natural oil,synthetic oil, wax, etc.

The polyolefin resin composition of the present invention can beproduced, for example, by a method in which the cycloolefin-basedpolymer (a) and the graft-modified elastomer (b) are separatelyprepared, a mixture of these cycloolefin-based polymer andgraft-modified elastomer (b) are melt-kneaded, further, the compound (c)having an amino group is incorporated into the kneaded mixture andfurther kneaded; by a method in which the cycloolefin-based polymer (a),the graft-modified elastomer (b) and the compound (c) having an aminogroup are melt-kneaded at one lot; and particularly by a method in whichthe graft-modified elastomer (b) and the compound (c) having an aminogroup are melt-kneaded, the resultant kneaded mixture is incorporatedinto the cycloolefin-based polymer (a) and further kneaded.

The above polyolefin resin composition containing the cycloolefin-basedpolymer (a), the graft-modified elastomer (b) and the compound (c)having an amino group, provided by the present invention, has asoftening temperature (TMA), measured with a thermal mechanicalanalyzer, of generally between 50° C. and 200° C., preferably between100° C. and 180° C.

The polyolefin resin composition of the present invention can be usednot only in fields where ordinary polyolefins are used but also infields where, for example, filler-reinforced PP, ABS resin and modifiedpolyphenylene oxide are used and mechanical strength is particularlyrequired.

The polyolefin resin composition of the present invention has astructure in which the graft-modified elastomer (b) is dispersed in thecycloolefin-based polymer (a). And it is considered that due to theincorporation of the compound (c) having an amino group, a structuresimilar to a crosslinked structure is formed in the interior of thegraft-modified elastomer (b). A molded article formed of such apolyolefin resin composition has excellent impact strength. Inparticular, due to the use of the compound having an amino group in themolecule, the contribution of the structure similar to a crosslinkedstructure decreases when the polyolefin resin composition is melted. Asa result, such a polyolefin resin composition exhibits excellentflowability, and moreover, a molded article therefrom has excellentimpact strength and gloss.

The present invention will be described below by reference to Examples.However, Examples shall not be construed as limitations to the presentinvention.

EVALUATION METHOD

Cycloolefin-based polymers, graft-modified elastomers and compoundshaving an amino group, used in the present invention, and polyolefinresin compositions of the present invention were measured for theirproperties as follows.

INTRINSIC VISCOSITY [η]

Measured in decalin at 135° C.

SOFTENING TEMPERATURE (TMA)

A temperature at which a needle having a diameter of 1 mm and a flat endpenetrates 100 μm deep at a temperature elevation rate of 5° C./minuteunder a load of 50 g was taken as a TMA.

CONTENT OF GRAFT MONOMER IN GRAFT-MODIFIED ELASTOMER

Measured by ¹³ C-NMR.

CRYSTALLINITY

Measured at 23° C. by an X-ray diffraction method.

TENSILE MODULUS

A press-formed test piece having a thickness of 2 mm was measured at 23°C. according to ASTM D638.

IZ IMPACT STRENGTH

A notched, injection-molded test piece having a thickness of 1/8 inchwas measured at 23° C. according to ASTM D256.

INITIAL FLEXURAL MODULUS (FM)

An injection-molded test piece having a thickness of 1/8 inch wasmeasured at a cross head speed of 20 mm/minute at 23° C. according toASTM D790.

FLEXURAL STRESS AT YIELD POINT (FS)

Measured in the same manner as in the measurement for FM according toASTM D790.

GLOSS

An injection-molded plate having a thickness of 2 mm was measured at anincident angle of 60 degrees at 23° C. according to ASTM D523.

MELT INDEX (MI)

Measured at 260° C. under a load of 2.16 kg according to JIS-K-6760.

PREPARATION EXAMPLE 1 Preparation of cycloolefin copolymer (a)

A copolymerization reaction of ethylene and tetracyclo[4.4.0.1²,5.1⁷,10]dodecene-3 (to be sometimes abbreviated as "TCD-3" hereinafter) wascontinuously carried out with a one-liter polymerizer having a stirringvane. That is, the polymerizer was continuously fed, from its top, witha cyclohexane solution of TCD-3 at a rate of 0.4 lit./hour such that theconcentration of TCD-3 in the polymerizer was 60 g/lit, a cyclohexanesolution of VO(OC₂ H₅)Cl₂ at a rate of 0.5 lit./hour such that theconcentration of vanadium in the polymerizer was 0.5 mmol/lit. (in thiscase the concentration of vanadium being fed was 2.86 times that ofvanadium in the polymerizer), a cyclohexane solution of ethylaluminumsesquichloride [Al(C₂ H₅)₁.5 Cl₁.5 ] at a rate of 0.4 lit./hour suchthat the concentration of aluminum in the polymerizer was 4.0 mmol/l,and cyclohexane at a rate of 0.7 lit./hour, while polymerizationreaction liquid was continuously withdrawn from the bottom of thepolymerizer such that the amount of polymerization liquid in thepolymerizer was constantly 1 lit. (that is, the residence time was 0.5hour).

Further, the reaction system was also fed with 30 lit./hour of ethylene,10 lit./hour of nitrogen and 0.3 lit./hour of hydrogen through abubbling tube.

The copolymerization was carried out at 10° C. with circulating acooling medium through a jacket externally provided to the polymerizer.

An ethylene TCD-3 random copolymer was prepared by carrying out thecopolymerization reaction under the above conditions.

That is, polymerization liquid was withdrawn from the bottom of thepolymerizer, and a cyclohexane/isopropyl alcohol mixed liquid (volumeratio=1/1) was added thereto to terminate the polymerization reaction.Then, an aqueous solution prepared by adding 5 ml of concentratedhydrochloric acid to 1 lit. of water and the above polymerizationsolution in a proportion of 1:1 were brought into contact by stirringthem vigorously with a homomixer thereby to transfer a catalyst residueto a water phase.

The above mixture was allowed to stand, and the water phase was removed.Then, the remainder was further washed with distilled water twice, andpurified and separated.

The resultant polymerization liquid was brought into contact, withvigorously stirring, with acetone of which the amount was three timesthat of the polymerization liquid, and a solid portion precipitated wasrecovered by filtration, and fully washed with acetone. Thereafter, therecovered solid was dried under a nitrogen current at 130° C. at 350mmHg for 24 hours. The above procedure was continuously carried out toprepare an ethylene.TCD-3 random copolymer at a rate of 76 g(38g/lit)/hour.

The above copolymer had an ethylene content, determined on the basis ofthe result of measurement by ¹³ C-NMR analysis, of 70 mol %. Further,this copolymer was measured for an intrinsic viscosity [η] in decalin at135° C. to show 0.61 dl/g, and it had an iodine value of 1.0 and TMA of115° C.

This cycloolefin random copolymer (a) is referred to as "PO-1"hereinafter.

PREPARATION EXAMPLE 2 Polymerization example of cycloolefin copolymer(a)

Preparation Example 1 was repeated except that the polymerizer was fedwith ethylene at a rate of 20 lit./hour and hydrogen at a rate of 0.5lit./hour, to prepare an ethylene.TCD-3 copolymer.

The above copolymer had an ethylene content, determined on the basis ofthe result of measurement by ¹³ C-NMR analysis, of 63 mol %. Further,this copolymer was measured for an intrinsic viscosity [η] in decalin at135° C. to show 0.5 dl/g, and it had an iodine value of 1.0 and TMA of150° C.

This cycloolefin random copolymer (a) is referred to as "PO-2"hereinafter.

PREPARATION EXAMPLE 3 Preparation example of cycloolefin copolymer (a)

Preparation Example 1 was repeated except that the polymerizer was fedwith ethylene at a rate of 20 lit./hour and hydrogen at a rate of 0.3lit./hour, to prepare an ethylene.TCD-3 copolymer.

The above copolymer had an ethylene content, determined on the basis ofthe result of measurement by ¹³ C-NMR analysis, of 63 mol %. Further,this copolymer was measured for an intrinsic viscosity [η] in decalin at135° C. to show 0.6 dl/g, and it had an iodine value of 1.0 and TMA of150° C.

This cycloolefin random copolymer (a) is referred to as "PO-3"hereinafter.

PREPARATION EXAMPLE 4 Preparation example of cycloolefin copolymer (a)

Preparation Example 1 was repeated except that the polymerizer was fedwith ethylene at a rate of 10 lit./hour and hydrogen at a rate of 0.3lit./hour, to prepare an ethylene.TCD-3 copolymer.

The above copolymer had an ethylene content, determined on the basis ofthe result of measurement by ¹³ C-NMR analysis, of 56 mol %. Further,this copolymer was measured for an intrinsic viscosity [η] in decalin at135° C. to show 0.8 dl/g, and it had an iodine value of 1.0 and TMA of170° C.

This cycloolefin random copolymer (a) is referred to as "PO-4"hereinafter.

PREPARATION EXAMPLE 5 Preparation example of graft-modified elastomer(b)

One part by weight of maleic anhydride and 0.2 part by weight of2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 were mixed with 100 parts byweight of an ethylene propylene copolymer having an ethylene content of80 mol % and an intrinsic viscosity [η], measured in decalin at 130° C.,of 2.2 dl/g (this copolymer will be referred to as "MP-0" hereinafter),and the resultant mixture was melt-kneaded at 260° C. with a twin-screwextruder equipped with a vent having a diameter of 30 mm to give agraft-modified elastomer (b).

The above-obtained graft-modified elastomer had a maleic anhydride graftamount of 0.90% by weight and a tensile modulus of 80 kg/cm².

The above graft-modified elastomer (b) is referred to as "MP-1"hereinafter.

PREPARATION EXAMPLE 6 Preparation example of graft-modified elastomer(b)

Preparation Example 5 was repeated except that the maleic anhydride wasreplaced with 1 part by weight, per 100 parts by weight of "MP-0", ofglycidyl methacrylate and that this glycidyl methacrylate was mixed with0.2 part by weight of 2,5-dimethyl-2,5-di(t-butylperoxy)-hexyne-3 togive a graft-modified elastomer (b).

The above-obtained graft-modified elastomer had a glycidyl methacrylategraft amount of 0.90% by weight and a tensile modulus of 80 kg/cm².

The above graft-modified elastomer (b) is referred to as "MP-2"hereinafter.

PREPARATION EXAMPLE 7 Preparation example of graft-modified elastomer(b)

1 Part by weight of maleic anhydride and 0.2 part by weight of2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 were mixed with 100 parts byweight of an ethylene propylene copolymer having an ethylene content of80 mol % and an intrinsic viscosity [η], measured in decalin at 130° C.,of 1.4 dl/g, and the resultant mixture was melt-kneaded at 260° C. witha twin-screw extruder equipped with a vent having a diameter of 30 mm togive a graft-modified elastomer (b).

The above-obtained graft-modified elastomer had a maleic anhydride graftamount of 0.98% by weight and a tensile modulus of 80 kg/cm².

The above graft-modified elastomer (b) is referred to as "MP-3"hereinafter.

PREPARATION EXAMPLE 8 Preparation example of a compound (c) having anamino group

Vacuum-dried ε-aminocaproic acid (to be referred to as PA-0 hereinafter)was kept at 170° C. under reduced pressure for 14 hours to give apolymer of PA-0. This polymer had an intrinsic viscosity [η], measuredin sulfuric acid at 25° C., of 0.4 dl/g.

The above compound having an amino group is referred to as "PA-1"hereinafter.

EXAMPLE 1

10 Parts by weight of the graft-modified elastomer (MP-1) obtained inPreparation Example 5 and 5 parts by weight of nylon-6 (trade name:Amilan CM1007, supplied by Toray Industries, Inc) as a compound havingan amino group were melt-kneaded at 250° C. with a twin-screw extruderequipped with a vent having a diameter of 30 mm to prepare a precursorcompound. This precursor substance and 85 parts by weight of thecycloolefin random copolymer (PO-1) obtained in Preparation Example 1were kneaded with the above extruder at 230° C. to give a polyolefinresin composition.

The resultant resin composition was dried at 100° C. for 8 hours, andthen test pieces and square bars for the measurements of physicalproperties were prepared therefrom with an injection molding machine (30EPN, supplied by Toshiba IS) at 250° C. at a mold temperature of 70° C.

Table 1 shows the physical properties of the test pieces.

As is clear from the results shown in Table 1, the above-obtainedcomposition was excellent in impact strength, rigidity, heat resistance,gloss and flowability.

COMPARATIVE EXAMPLE 1

Example 1 was repeated except that 15 parts by weight of thegraft-modified elastomer (MP-1) obtained in Preparation Example 5 and 85parts by weight of the cycloolefin random copolymer (PO-1) obtained inPreparation Example 1 were melt-kneaded with a twin-screw extruderequipped with a vent having a diameter of 30 mm at 230° C. without usingAmilan CM1007 to give a polyolefin resin composition. Test pieces andsquare bars were prepared from this resin composition in the same manneras in Example 1, and evaluated on physical properties.

Table 1 shows the physical properties of the test pieces.

As is clear from the results shown in Table 1, this composition showedexcellent flowability, and the test pieces formed from this compositionwere excellent in rigidity and heat resistance. However, the impactstrength thereof was low.

EXAMPLE 2

85 Parts by weight of the cycloolefin copolymer (PO-1) obtained inPreparation Example 1, 10 parts by weight of the graft-modifiedelastomer (MP-1) and 5 parts of a compound having an amino group(CM1007) were melt-kneaded with the above extruder in the same manner asin Example 1 without preparing a precursor mixture to obtain apolyolefin resin composition. Test pieces and square bars were preparedfrom this resin composition in the same manner as in Example 1, andevaluated on their physical properties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the test pieces formedfrom this composition were excellent in impact strength, rigidity, heatresistance and gloss, and the composition was also excellent inflowability.

EXAMPLE 3

Example 1 was repeated except that the graft-modified elastomer waschanged to MP-2 to prepare a polyolefin resin composition. Test piecesand square bars were prepared from this resin composition in the samemanner as in Example 1, and evaluated on their properties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the test pieces formedfrom this composition were excellent in impact strength, rigidity, heatresistance and gloss, and the composition was also excellent inflowability.

COMPARATIVE EXAMPLE 2

Example 1 was repeated except that 15 parts by weight of thegraft-modified elastomer (MP-2) and 85 parts by weight of thecycloolefin random copolymer (PO-1) were melt-kneaded with a twin-screwextruder equipped with a vent having a diameter of 30 mm at 230° C.without using CM1007 to give a polyolefin resin composition. Test piecesand square bars were prepared from this resin composition in the samemanner as in Example 1 and evaluated on their physical properties.

Table 1 shows the physical properties of the test pieces.

As is clear from the results shown in Table 1, this composition showedexcellent flowability, and the test pieces formed from this compositionwere excellent in rigidity and heat resistance. However, the impactstrength thereof was low.

EXAMPLE 4

Example 1 was repeated except that the graft-modified elastomer wasreplaced with MP-3 to prepare a polyolefin resin composition. Testpieces and square bars were prepared from this resin composition in thesame manner as in Example 1, and evaluated on their properties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the test pieces formedfrom this composition were excellent in impact strength, rigidity, heatresistance and gloss, and the composition was also excellent inflowability.

COMPARATIVE EXAMPLE 3

15 Parts by weight of the graft-modified elastomer (MP-3) and 85 partsby weight of the cycloolefin random copolymer (PO-1) were melt-kneadedat 230° C. with an twin-screw extruder equipped with a vent having adiameter of 30 mm in the same manner as in Example 1 without usingCM1007 to obtain a polyolefin resin composition. Test pieces and squarebars were prepared from this resin composition in the same manner as inExample 1, and evaluated on their physical properties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the above composition wasexcellent in flowability and the test pieces formed from thiscomposition were excellent in rigidity and heat resistance. However,their impact strength was low.

EXAMPLE 5

14 Parts by weight of the graft-modified elastomer (MP-1) obtained inPreparation Example 5 and 1 part by weight of "PA-1" as a compoundhaving an amino group were melt-kneaded at 250° C. with a twin screwextruder equipped with a vent having a diameter of 30 mm to prepare aprecursor mixture. This precursor substance and 85 parts by weight ofthe cycloolefin random copolymer (PO-1) obtained in Preparation Example1 were melt-kneaded with the above extruder to give a polyolefin resincomposition.

Test pieces and square bars were prepared from this resin composition inthe same manner as in Example 1, and evaluated on their physicalproperties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the test pieces formedfrom this composition were excellent in impact strength, rigidity, heatresistance and gloss, and the composition was also excellent inflowability.

EXAMPLE 6

12 Parts by weight of the graft-modified elastomer (MP-1) obtained inPreparation Example 5 and 3 parts by weight of "PA-1" obtained inPreparation Example 8 as a compound having an amino group weremelt-kneaded at 250° C. with a twin-screw extruder equipped with a venthaving a diameter of 30 mm to prepare a precursor mixture. Thisprecursor substance and 85 parts by weight of the cycloolefin randomcopolymer (PO-1) obtained in Preparation Example 1 were kneaded with theabove extruder at 230° C. to give a polyolefin resin composition. Testpieces and square bars were prepared from this resin composition in thesame manner as in Example 1, and evaluated on their physical properties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the test pieces formedfrom this composition were excellent in impact strength, rigidity, heatresistance and gloss, and the composition was also excellent inflowability.

EXAMPLE 7

10 Parts by weight of the graft-modified elastomer (MP-1) obtained inPreparation Example 5 and 5 parts by weight of a compound having anamino group, Amilan (CM1007), were melt-kneaded at 250° C. with atwin-screw extruder equipped with a vent having a diameter of 30 mm toprepare a precursor mixture. This precursor substance and 85 parts byweight of the cycloolefin random copolymer (PO-2) obtained inPreparation Example 2 were kneaded with the above extruder at 230° C. togive a polyolefin resin composition.

Test pieces and square bars were prepared from this resin composition inthe same manner as in Example 1, and evaluated on their physicalproperties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the test pieces formedfrom this composition were excellent in impact strength, rigidity, heatresistance and gloss, and the composition was also excellent inflowability.

COMPARATIVE EXAMPLE 4

15 Parts by weight of the graft-modified elastomer (MP-1) and 85 partsby weight of the cycloolefin random copolymer (PO-2) were melt-kneadedat 230° C. with an twin-screw extruder equipped with a vent having adiameter of 30 mm in the same manner as in Example 7 without usingCM1007 to obtain a polyolefin resin composition. Test pieces and squarebars were prepared from this resin composition in the same manner as inExample 1, and evaluated on their physical properties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the above composition wasexcellent in flowability and the test pieces formed from thiscomposition were excellent in rigidity and heat resistance. However,their impact strength was low.

EXAMPLE 8

10 Parts by weight of the graft-modified elastomer (MP-1) obtained inPreparation Example 5 and 10 parts by weight of a compound having anamino group, Amilan (CM1007), were melt-kneaded at 250° C. with atwin-screw extruder equipped with a vent having a diameter of 30 mm toprepare a precursor mixture. This precursor substance and 80 parts byweight of the cycloolefin random copolymer (PO-2) obtained inPreparation Example 2 were kneaded with the above extruder at 230° C. togive a polyolefin resin composition.

Test pieces and square bars were prepared from this resin composition inthe same manner as in Example 1, and evaluated on their physicalproperties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the test pieces formedfrom this composition were excellent in impact strength, rigidity, heatresistance and gloss, and the composition was also excellent inflowability.

EXAMPLE 9

12 Parts by weight of the graft-modified elastomer (MP-1) obtained inPreparation Example 5 and 3 parts by weight of a compound having anamino group (PA-1) obtained in Preparation Example 8 were melt-kneadedat 250° C. with a twin-screw extruder equipped with a vent having adiameter of 30 mm to prepare a precursor mixture. This precursorsubstance and 85 parts by weight of the cycloolefin random copolymer(PO-3) obtained in Preparation Example 3 were kneaded with the aboveextruder at 230° C. to give a polyolefin resin composition.

Test pieces and square bars were prepared from this resin composition inthe same manner as in Example 1, and evaluated on their physicalproperties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the test pieces formedfrom this composition were excellent in impact strength, rigidity, heatresistance and gloss, and the composition was also excellent inflowability.

EXAMPLE 10

10 Parts by weight of the graft-modified elastomer (MP-1) obtained inPreparation Example 5 and 5 parts by weight of a compound having anamino group, Amilan (CM1007), were melt-kneaded at 250° C. with atwin-screw extruder equipped with a vent having a diameter of 30 mm toprepare a precursor mixture. This precursor substance and 85 parts byweight of the cycloolefin random copolymer (PO-3) obtained inPreparation Example 3 were kneaded with the above extruder at 230° C. togive a polyolefin resin composition.

Test pieces and square bars were prepared from this resin composition inthe same manner as in Example 1, and evaluated on their physicalproperties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the test pieces formedfrom this composition were excellent in impact strength, rigidity, heatresistance and gloss, and the composition was also excellent inflowability.

COMPARATIVE EXAMPLE 5

15 Parts by weight of the graft-modified elastomer (MP-1) and 85 partsby weight of the cycloolefin random copolymer (PO-3) were melt-kneadedat 230° C. with an twin-screw extruder equipped with a vent having adiameter of 30 mm in the same manner as in Example 10 without usingCM1007 to obtain a polyolefin resin composition. Test pieces and squarebars were prepared from this resin composition in the same manner as inExample 1, and evaluated on their physical properties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the above composition wasexcellent in flowability and the test pieces formed from thiscomposition were excellent in rigidity and heat resistance. However,their impact strength was low.

EXAMPLE 11

10 Parts by weight of the graft-modified elastomer (MP-1) obtained inPreparation Example 5 and 5 parts by weight of a compound having anamino group, Amilan (CM1007), were melt-kneaded at 250° C. with atwin-screw extruder equipped with a vent having a diameter of 30 mm toprepare a precursor mixture. This precursor substance and 85 parts byweight of the cycloolefin random copolymer (PO-4) obtained inPreparation Example 4 were kneaded with the above extruder at 230° C. togive a polyolefin resin composition.

Test pieces and square bars were prepared from this resin composition inthe same manner as in Example 1, and evaluated on their physicalproperties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the test pieces formedfrom this composition were excellent in impact strength, rigidity, heatresistance and gloss, and the composition was also excellent inflowability.

COMPARATIVE EXAMPLE 6

15 Parts by weight of the graft-modified elastomer (MP-1) and 85 partsby weight of the cycloolefin random copolymer (PO-4) were melt-kneadedat 230° C. with an twin-screw extruder equipped with a vent having adiameter of 30 mm in the same manner as in Example 11 without usingCM1007 to obtain a polyolefin resin composition. Test pieces and squarebars were prepared from this resin composition in the same manner as inExample 1, and evaluated on their physical properties.

Table 1 shows the physical properties of the above-obtained test pieces.

As is clear from the results shown in Table 1, the above composition wasexcellent in flowability and the test pieces formed from thiscomposition were excellent in rigidity and heat resistance. However,their impact strength was low.

                                      TABLE 1                                     __________________________________________________________________________           Cycloolefin                                                                           Graft  Compound                                                                             Resin                                                   randum  modified                                                                             having amino                                                                         composition                                                                          IZ     FM   MI    Gloss                                                                             TMA                        copolymer (a)                                                                         elastomer (b)                                                                        group (c)                                                                            (a)/(b)/(c)                                                                          (kg · cm/cm)                                                                (kg/cm.sup.2)                                                                      (g/10 min.)                                                                         (%) (°C.)        __________________________________________________________________________    Ex. 1  PO-1    MP-1   CM1007 85/10/5                                                                              53     22000                                                                              15    97  112                 Com. Ex. 1                                                                           PO-1    MP-1   --     85/15/0                                                                               6     21000                                                                              15    93  114                 Ex. 2  PO-1    MP-1   CM1007 85/10/5                                                                              50     19000                                                                              15    95  112                 Ex. 3  PO-1    MP-2   CM1007 85/10/5                                                                              41     20000                                                                              13    95  111                 Com. Ex. 2                                                                           PO-1    MP-2   --     85/15/0                                                                               6     22000                                                                              15    95  114                 Ex. 4  PO-1    MP-3   CM1007 85/10/5                                                                              40     21000                                                                              15    95  111                 Com. Ex. 3                                                                           PO-1    MP-3   --     85/15/0                                                                               6     22500                                                                              16    97  113                 Ex. 5  PO-1    MP-1   PA-0   85/14/1                                                                              52     21000                                                                              15    95  111                 Ex. 6  PO-1    MP-1   PA-1   85/12/3                                                                              45     20500                                                                              15    95  112                 Ex. 7  PO-2    MP-1   CM1007 85/10/5                                                                              12     23500                                                                              26    97  148                 Com. Ex. 4                                                                           PO-2    MP-1   --     85/15/0                                                                               3     23600                                                                              27    95  149                 Ex. 8  PO-2    MP-1   CM1007   80/10/10                                                                           20     20000                                                                              27    97  145                 Ex. 9  PO-3    MP-1   PA-1   85/12/3                                                                              14     23000                                                                              27    95  149                 Ex. 10 PO-3    MP-1   CM1007 85/10/5                                                                              15     23400                                                                              4     93  149                 Com. Ex. 5                                                                           PO-3    MP-1   --     85/15/0                                                                               5     23000                                                                              4     92  148                 Ex. 11 PO-4    MP-1   CM1007 85/10/5                                                                              25     23000                                                                              0.2   90  168                 Com. Ex. 6                                                                           PO-4    MP-1   --     85/15/0                                                                               6     23300                                                                              0.3   93  167                 __________________________________________________________________________

We claim:
 1. A polyolefin resin composition comprising:(a) at least onecycloolefin-based polymer selected from the group consisting of(a1) ahomopolymer derived from a cycloolefin represented by the followingformula (I): ##STR22## wherein n is 0 or 1, m is 0 or a positiveinteger, q is 0 or 1, each of R¹ to R¹⁸, R^(a) and R^(b) is,independently of the other, an atom or a group selected from the classconsisting of a hydrogen atom, a halogen atom and a hydrocarbongroup,two of R¹⁵ to R¹⁸ may bond to each other to form a monocyclic orpolycyclic group which may have a double bond, and further, acombination of R¹⁵ and R¹⁶ or a combination R¹⁷ and R¹⁸ may form analkylidene group, (a2) a copolymer derived from said cycloolefins ofsaid formula (I), (a3) a hydrogenation polymer of the homopolymer (a1)or the copolymer (a2), and (a4) a cycloolefin/ethylene random copolymercomposed of a polymer unit derived from a cycloolefin of said formula(I) and a polymer unit of ethylene; (b) an elastomer which is agraft-modified product of a non-crystalline or low-crystalline α-olefincopolymer formed from at least two α-olefins grafted with an unsaturatedcarboxylic acid or a derivative thereof, and which is dispersed in thecomponent (a) and has a tensile modulus, at 23° C., of 0.1 to 2,000kg/cm², and (c) a compound which has one amino group in the molecule andforms a structure similar to a crosslinked structure in the interior ofthe compound (b) and wherein the polyolefin resin composition contains,per 100 parts by weight of the total amount of the components (a), (b)and (c), 50 to 95 parts by weight of the component (a), 1 to 50 parts byweight of the component (b) and 0.01 to 45 parts by weight of thecomponent (c).
 2. The polyolefin resin composition of claim 1, whereinthe component (a) has a softening temperature in the range between 70°C. and 200° C. and the component (a) has an intrinsic viscosity [η],measured in decalin at 130° C., in the range of 0.3 to 2.0 d1/g.
 3. Thepolyolefin resin composition of claim 1, wherein the compound (c) havingone amino group in the molecule is ε-aminocaproic acid or a condensatethereof, or nylon-6.
 4. The polyolefin resin composition of claim 1,wherein the compound (c) having one amino group in the molecule isselected from the group consisting of:(C1) a condensate having one aminogroup in the molecule; (C2) a ring-opening reaction product having oneamino group in the molecule: (C3) a polymer in which one amino group isbonded to a polyolefin having a molecular weight of not less than20,000; and (C4) a low molecular weight amino compound in which aterminus end of the molecule is an amino group.
 5. The polyolefin resincomposition of claim 4 wherein the compound (c) having one amino groupin the molecule is said condensate (C1).
 6. The polyolefin resincomposition of claim 4 wherein the compound (c) having one amino groupin the molecule is said ring-opening reaction product (C2).
 7. Thepolyolefin resin composition of claim 4 wherein the compound (c) havingone amino group in the molecule is said polymer (C3).
 8. The polyolefinresin composition of claim 4 wherein the compound (c) having one aminogroup in the molecule is said low molecular weight amino compound (C4).9. The polyolefin resin composition of claim 4 wherein the elastomer (b)is a graft-modified ethylene-α-olefin copolymer rubber.
 10. Thepolyolefin resin composition of claim 4 wherein the elastomer (b) is agraft-modified propylene-α-olefin copolymer rubber.
 11. The polyolefinresin composition of claim 4 wherein the component (c) is present in anamount of 0.01 to 30 parts by weight.
 12. The polyolefin resincomposition of claim 4 wherein the components (b) and (c) aremelt-kneaded with each other to form a precursor substance, and theprecursor substance and component (a) are thereafter melt-kneaded toform said composition.